Process or preparing hydrophobic cellulose fibers



Patented Mar. 22, 1938 PROCESS 0R PREPARING HYDROPHOBIC CELLULOSE FIBERS Fritz Slefert, Oppau, and Joseph Stadler, Ludwigshafen-on-the-Rhin e, Germany, assignors to 1., G. Farbenindustrie Aktiengesellschai't, Franktort-on-the-Main, Germany No Drawing.

Application September 24, 1936,

Serial 'No. 102,300. In Germany September 28,

4 Claims.

The presentin'vention relates to a process of preparing hydrophobic cellulose fibers.

In patent application Serial No. 81,122, filed May 21, 1936, (Franz Emil Hubert et al.-Process of imparting hydrophobic properties to cellulose fibers) is described a process for making cellulose fibers hydrophobe by applying to the fibers or incorporating in them a compound which contains at least one aliphatic or cycloaliphatic residue having at least 4 carbon atoms and capable of reacting with an aldehyde, for instance an amine of this constitution, and simultaneously or subsequently treating the fibers with an aliphatic aldehyde.

We have found that particularly good hydrophobic properties may be imparted to cellulose fibers by incorporating with them a water-soluble salt of an amine of the constitution prescribed in the said patent application and simultaneously 0 or subsequently treating them with an aliphatic aldehyde in the absence of an appreciable quantity of free acid.

In the process of the present invention there may suitably be used, for instance, the salts of stearylamine, octylamine, dodecylamine, cetylamine, oleylamine, ricinolamine, as well as the substitution products of these amines, for instance chlorocetylamine or the like. There are also suitable the salts of amines, the high molecular alkyl radicals of which are interrupted by heteroatoms or atom groups, for instance, acid amide groups; there may for instance be named the ethylenediamino-monostearic acid amide and the N-octodecyl-ethylene-diamine.

The use of salts in preference to the free amines in this process has the advantage that on account of their solubility in-water they are essentially more easily and economically to be applied. By the present invention it is possible to avoid the use of an organic solvent or even operation in aqueous .dispersion. When water-sol- 'uble salts of amines are used the treatment baths are very permanent and, in contrast with the emulsions of free amines, show no tendency to throw up cream or form precipitates.

The hydrophobe eiiect obtainable by the process may be considerably improved by adding to the treatment bath, in addition to the aforesaid compounds, compounds of lower molecular weight which contain in the molecule several aminoor iminogroups, or nitrogen atoms. As such further compounds may be named: 1.3.5-triazine and its derivatives, for example melamine, ammeline, ammelide and hexamethylene-tetramine; ethylene-diamine; urea, thiourea; guanidine, bigua- 'nide, guanyl-urea; cyanuric acid; biuret or the technical product obtainable by prolonged heating, for instance for 12-48 hours, of urea or thiourea at a temperature of about 160 (3.; dicyandiamide, dicyandiamidine, thiodicyandiamidine, sodium cyanamide; ortho-, paraor meta-phenylene-diamine; diaminopyridine or its derivatives and substitution products, for instance its methylol-compounds. These additions may also be made with great advantage in the process of the aforesaid patent application.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto.

.(1) In an aqueous liquor containing per liter 2 grams of melamine, 5 grams of stearylamine-acetate and 50 cc. of aqueous formaldehyde solution of 30 per cent strength, cotton piece goods are treated on a reel for 15 minutes; they are then centrifuged and dried for about 1 hour at 100 C.

The goods thus treated have a remarkable hydrophobe character, which is stable to treatment with boiling soap liquor (washing). The treating liquor keeps well and is still useful for impregnation purposes even after standing for several days.

(2) In a liquor containing per liter 5 grams of stearylamine-acetate, 5 grams of meta-phenylene-diamine and 100 cc. of an aqueous solution of formaldehyde of 30 per cent strength, artificial silk knitted goods are treated for 5 minutes at room temperature. They are then centrifuged and dried for half an hour at 100 C. This treatment imparts a hydrophobe efiect which is remarkably stable to washing.

(3) Acetate silk piece-goods are treated on the foulard with a liquor containing per liter 10 grams of stearylamine-acetate, 10 grams of melamine and 50 cc. of an aqueous formaldehyde solution of 30 per cent strength and are then wrung out. They are'then dried, preliminarily at 50-60 C., and finally for half an hour at about 100 C. The acetate silk thus treated has quite a surprising hydrophobe effect.

(4) In a bath containing per liter of water 5 grams of hexamethylene-tetramine, 5 grams of stearyl-amine-lactate and 50 cc. of formaldehyde of 30 per cent strength, a mixed tissue made from 70 per cent of wool and 30 per cent of staple fiber is treated at room temperature for 10 minutes, in a proportion of the goods to the liquor 1: 40; the tissue is then centrifuged and dried for 1 hour at 100 C. The tissue thus treated has a very good hydrophobe effect.

(5) In a bath containing per liter of water 2 rams of melamine, 5 grams of the formate of the condensation product of ethylene-diamino-monstaple fiber is treated at about 30 C. Thereupon,

the fabric is centrifuged, dried at 60 C. and'then heated for 30 minutes at 110 C. The fabric treated in this manner has a good hydrophobe effect, which property is not aflected by washing in the usual manner.

(6) In a bath containing per liter of water 5 grams of guanidine hydrochloride, 5 grams of cetyl-amine-formate and cc. of formaldehyde of 30 per cent strength, loose staple fiber is treated for 30 minutes at room temperature. After this treatment, the material is centrifuged and after drying at -60" C. it is heated for 1 hour at C. The material thus treated has a good hydrophobe effect.

(7) In a bath containing per liter of water 5 grams of dicyandiamlde, 3 grams of the acetate of N-octodecyl-ethylene-diamine and 25 cc. of formaldehyde of 30 per cent strength, a fabric made from 60 per cent of cotton and 40 per cent of staple fiber is treated on the vat winch for half an hour at room temperature. The fabric is then centrifuged and dried for 1 hour at C. The fabric treated in this manner has a high hydrophobe effect which is retained even on washing with soap and sodium carbonate.

What we claim is:

1. A process of preparing hydrophobic cellulose fibers by impregnating them with a bath which contains water-soluble salts of amines containing at least one aliphatic or cycloaliphatic radical with at least 4 carbon atoms and being capable of reacting with aldehydes, a low molecular compound containing several amino groups and an aliphatic ald :-i-.yde, and heating after the impregnating process.

2. A process of preparing hydrophobic cellulose fibers by impregnating them with a bath which contains water-soluble salts of amines containing at least one aliphatic or cycloaliphatic radical with at least 4 carbon atoms and being capable of reacting with aldehydes, a low molecular compound containing several imino groups and an aliphatic aldehyde, and heating after the impregnating process.

3. A process of preparing hydrophobic cellulose fibers by impregnating them with a bath which contains water-soluble salts of amines containing at least one aliphatic or cycloaliphatic radical with at least 4 carbon atoms and being capable of reacting with aldehydes, a low molecular compound containing several nitrogen atoms ln the molecule and an aliphatic aldehyde, and heating after the impregnating process.

4. Hydrophobic cellulose fibers containing condensation products of low molecular aliphatic compounds containing several amino groups, allphatic aldehydes and water-soluble salts of amines containing at least one aliphatic or cycloaliphatic radical with at least 4 carbon atoms and being capable of reacting with aldehydes.

FRITZ SIEFERT. JOSEPH STADLER. 

